EP2807130B1 - Mortier de protection contre l'incendie - Google Patents
Mortier de protection contre l'incendie Download PDFInfo
- Publication number
- EP2807130B1 EP2807130B1 EP14703051.4A EP14703051A EP2807130B1 EP 2807130 B1 EP2807130 B1 EP 2807130B1 EP 14703051 A EP14703051 A EP 14703051A EP 2807130 B1 EP2807130 B1 EP 2807130B1
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- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- fire protection
- cement
- test
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000004224 protection Effects 0.000 title claims description 30
- 239000004570 mortar (masonry) Substances 0.000 title claims description 24
- 239000004568 cement Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000010451 perlite Substances 0.000 claims description 14
- 235000019362 perlite Nutrition 0.000 claims description 14
- 239000010445 mica Substances 0.000 claims description 12
- 229910052618 mica group Inorganic materials 0.000 claims description 12
- 239000010455 vermiculite Substances 0.000 claims description 11
- 229910052902 vermiculite Inorganic materials 0.000 claims description 11
- 235000019354 vermiculite Nutrition 0.000 claims description 11
- 229910021532 Calcite Inorganic materials 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 239000011490 mineral wool Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- -1 sulfur aluminate Chemical class 0.000 claims description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000013008 thixotropic agent Substances 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000008030 superplasticizer Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 50
- 239000007921 spray Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 239000000047 product Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 101100184147 Caenorhabditis elegans mix-1 gene Proteins 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 3
- 229910001678 gehlenite Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000001073 sample cooling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5027—Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/006—Aspects relating to the mixing step of the mortar preparation involving the elimination of excess water from the mixture
- C04B40/0064—Processes of the Magnini or Hatscheck type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/4596—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with fibrous materials or whiskers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to fire protection mortar and its use for fire protection.
- the Rf RWS fire curve is used in Netherlands for tunnel fire protection. It is based on the realistic tunnel fire caused by a tank truck in a tunnel which may lead to severe concrete spalling and consequently damage tunnel stability. The tunnel concrete lining therefore must be protected to ensure public mobility and safety.
- the fire curve reaches ca 1200°C already in ca 5 min, then progressively increase to 1350°C in 60 min, afterwards it slowly decreases to 1200°C at 120 min.
- the test criteria allow the maximum temperature (T max ) at 380°C on concrete surface, and only 250°C at 25 mm inside the concrete surface. For drilled tunnels, the T max should not exceed 200-250°C (cf.
- the material used for tunnel fire protection must withstand the thermal shock, be resistant to abrasion necessary for tunnel cleaning, and insensitive to freeze/thaw attack.
- it should be free of quartz and with low energy consumption for reasons of environmental protection and green footprint.
- EP 0 986 525 of MBT Holding discloses a spray composition comprising mainly a cementitious binder, a thermally treated shell sand and additives necessary for spray operation.
- the mortar is commercially available under the trade designation Meyco Fireshield 1350, with a cured density at ca 1500 kg/m 3 .
- the material can pass the Rf RWS test but at a thickness of 40 to 50 mm. The combination of high density and large thickness makes the spray operation difficult, especially when the spray has to cover complex profiles, such as steel frameworks.
- EP 1 001 000 of Thermal Ceramics describes a spray which is claimed suitable for tunnels and it contains saw dust that releases smoke at high temperatures.
- This material has been on the market under the designation FireBarrier 135. It employs aluminate cement and kaolin, with a cured density of ca 1100 kg/m 3 , which is not only expensive, but also shrinks upon strong heating to such a degree that the product becomes cracked, a thick 38.5 mm has to be sprayed to survive the Rf RWS test, when tested by the TNO fire laboratory of Nederland.
- Promat fire protection materials for tunnel fire protection are known on the market.
- EP 1 326 811 of Promat teaches a fire protection board in composition of aluminate cement, xonotlite, functional fillers and additives. It has excellent performance in Rf RWS condition, however it uses high aluminate cement as binder, the cost and energy consumption of raw materials are high.
- the CAFCO FENDOLITE ® MII is a Promat spray fulfilling the Rf RWS condition. It comprises mainly of OPC and exfoliated vermiculite. This fire protection spray has been established worldwide, but supply of good vermiculite becomes increasingly difficult. Only a few vermiculite mines are known as asbestos free, their deposits are declining as result of industrial exploration, market prices are soaring.
- CN 101863640 A provides an environment-friendly colored fire-proof coating for tunnels, comprising the following components in parts by mass: 10-50 parts of cement, 40-90 parts of expanded perlite, expanded vermiculite and precipitated calcium carbonate, 1-10 parts of inorganic mineral fibers, 5-30 parts of flame retardant systems, 0.1-5.0 parts of rubber powder, 0.5-3.0 parts of water reducing agents, air entraining agents and expanding agents and 0.5-2.0 parts of inorganic pigments.
- CN101863640A range average total average wt% cement 10-50 30 24.3 inorganic mineral fibre 1-10 5 4.0 perlite/vermiculite/PCC (CaCO 3 ) 40-90 65 52.6 Al(OH) 3 /Mg(OH)2 5-30 17.5 14.2 gelling agent 0.1-5 2.5 2.0 air entrainer/foaming agent/plasticizer 0.5-3 2.5 2.0 pigment 0.5-2.0 1 0.8 Average composition of CN101863640 (A )
- the amount of cement after normalization to 100 weight-% is in the range of 8 to 40 weight %. This material is intended to be stable up to 1100°C.
- composition for the preparation of a fire protection mortar comprising
- the product after preparing a mortar and sprayed or casted and cured will have satisfactory mechanical properties and good freeze/thaw resistance in fully exposed condition according to EN12467.
- the cement, mica, and calcite react together to form refractory crystalline phases containing mainly Alite (C3S), Belite (C2S) and Gehlenite (C2AS) that are stable in the range of 1250-1400°C and capable to provide with passive fire protection in Rf RWS condition.
- C3S Alite
- Belite C2S
- C2AS Chalenite
- refractoriness at such high temperatures is obtained by a binder based on aluminate cement or ceramics.
- the cured material according to the invention can dehydrate and/or react in a stepwise manner within a temperature range of 70-1250°C, therefore capable of absorbing the heat step by step and diminishing the heat transfer and temperature increase in the substrate to be protected.
- the cement binder of the present invention can be preferably selected from the group consisting of Portland cement (CEM I), Portland composite cement (CEM II), Blastic furnace slag cement (CEM III), Pozzolanic cement (CEM IV), other Composite cement (CEM V) according to EN 197-1and combinations thereof.
- CEM I Portland cement
- CEM II Portland composite cement
- CEM III Blastic furnace slag cement
- CEM IV Pozzolanic cement
- CEM V other Composite cement
- OPC Ordinary Portland Cement
- the calcite of the invention includes all forms of CaCO 3 and its polymorphs such as Aragonite and Vaterite, it can be either grounded calcium carbonate (GCC) or precipitated calcium carbonate (PCC), used alone or in combination thereof.
- GCC grounded calcium carbonate
- PCC precipitated calcium carbonate
- the CaCO 3 decomposes at ca 850°C to form CaO and CO 2 .
- the CO 2 gas has lower thermal conductivity than air at high temperatures, it improves thermal insulation.
- the CaO reacts with cement and mica to form required refractory phases.
- Preferred average particle size ranges up to 200 ⁇ m. If CEM II, CEM III, CEM IV or CEM V are used which contain CaCO 3 already, the calcite dosing of the composition should be adapted accordingly to avoid residual CaO from the high temperature reaction.
- hydrated lime or Ca(OH) 2 should not be used in the present invention.
- the Ca(OH) 2 facilitates formation of ettringite during cement hydration, which affects formation of optimal combination of C2S/C3S/C2AS refractory phases at high temperatures, leads to inferior thermal insulation and/or stability during the fire test.
- the third ingredient of the invention is mica, e.g. selected from the group consisting of muscovite, phlogopite or biotite.
- the mica leads to better mechanical properties and diminishes thermal shrinkage, at temperature > 1200°C, it decomposes and reacts with cement and CaO to form the Alite, Belite and Gehlenite, therefore provides with material stability.
- this high temperature reaction consumes also large amount of energy which reduces the heat flow from fire side to the cold side.
- the range of mica is 8-20%, particle size is below 3 mm. Beyond of this range, either the mica shows no effect; or the sprayability will be affected.
- the composition comprises xonotlite, preferably not more than 5 weight %.
- the xonotlite provides with both thermal insulation and thermal stability at high temperatures. It is spherical particles made by a slurry reactor in autoclaving condition as disclosed in the EP 1 326 811 . However, according to the invention, needle-shaped materials may also be employed, such as, for example, the by-product in the processing of the spherical xonotlite.
- the xonotlite dehydrates at ca 800°C and then converts to wollastonite. This dehydration is a strongly endothermic reaction and consumes much energy.
- the wollastonite formed thereby has a theoretical melting point at 1530°C, it offers extra thermal stability in addition to the aforementioned refractory phases. Presence of spherical xonotlite in the invention is up to 5% by weight, in order to keep low cost and good sprayability.
- Expanded perlite is a light weight agent, it has low cost and is available worldwide. At temperatures below 900°C, it reduces the spray density meanwhile helps thermal insulation; at temperature above 900°C the perlite softens and acts as flux, promotes the solid-solid reaction among cement-CaO-Mica to form refractory phases of this invention.
- Preferred perlite dosing is 1-20%, packing density in range of 50-200 kg/m 3 , particle size below 6 mm, for the best pumpability and service life of the spray machine.
- expanded perlite is a preferred lightweight filler
- other fillers such as, e.g. pumice, foamed glass, hollow ceramic spheres from fly ash of power plant.
- Exfoliated vermiculite can also be used, though not the first choice of present invention.
- compositions are fibers.
- the fibers of this invention play important role in the material. During spray process, presence of the fibers bridges surrounding mixture. Together with action of thixotropic agent, they effectively keep the wet spray in place, the trowel finish can easily be obtained. During curing, the fibers help to reduce setting shrinkage and avoid surface cracks from the spray. When cured, the fibers function as reinforcement to improve material durability.
- the fibers are selected from the group consisting of, e.g. PP fiber, PVA fiber, cellulose fiber, glass fiber including alkali resistant glass fiber, rock wool or mineral wool, steel fibers. Preferred fiber dosing is 0.1 to 10 wt.-%, fiber length is below 15 mm.
- metal mesh or plastic mesh can be used inside of the mortar to secure a good bonding between the spray and substrate to avoid material fatigue during ageing.
- Commonly used additives are present in the invention to facilitate mixing, slurry pumping, sprayability, setting regulation, and durability. They are selected from the group consisting of setting accelerator, setting retarder, super plasticizer, water retention agent, thixotropic agent, pumping aid, water repellent, and re-dispersible polymers, used alone or in combination. Commonly used additives in the field can be employed, dosing is 0.01-4%.
- Air entrainer and/or foaming agent of present invention help not only mixing and slurry pumping, but also the frost resistance of cured spray by creating small capillary pores to avoid the material damage during freeze thaw cycles, when tested in fully water saturated conditions exposing to temperature change from 20°C to -20°C for 100 cycles, such as described by the standard EN12467.
- the preferred dosing is 0.01-2%.
- the composition of the present invention is a powder mixture. When mixed with water, it forms a fire protection mortar. Depending on the proposed use, the viscosity of the mortar can be adjusted by adding more or less water.
- the ratio of dry mix to water is 30 to 70 wt.-% dry mix and 70 to 30 wt.-% of water.
- the ratio of dry mix to water is 30 to 70 wt.-% dry mix and 70 to 30 wt.-% of water.
- a further embodiment of the invention is a fire protection product which is obtained by hydraulic setting of the fire protection mortar of the invention after spraying or casting.
- the bulk density is below 1200 kg/m 3 and preferably between 500 and 1000 kg/m 3 .
- the material according to the invention may also be used as a repair or joint mortar to fill in broken-off or burnt-out parts of the material, ensuring the same or similar properties of whole protection areas.
- the current invention can also be used to produce a board or panel, by spray or casting, followed by further shaping to form a monolithic body by, such as, Filter press, Flow-on and Magnani process.
- the cementitious mortar of present invention is intended for the most stringent fire test, such as the Rf RWS and Rf HCM condition. Obviously, it can also withstand less severe fire scenarios, such as the Rf RABT, Rf HC and Rf ISO conditions according to the standard EN 1363-1 and ISO 834-1, as illustrated in the Figure 1 .
- test compositions and test results are in the tables 1-2, all part by weight.
- the test-1 is according to present invention; the FB 135 is the commercially available product Fire Barrier 135 spray.
- the ingredients of table 1 and balanced water are mixed together by a planetary mixer to form a homogeneous cementitious mortar, then sprayed into a mould by a spray machine.
- key properties relevant to the fire protection i.e., density, bending strength and thermal shrinkage at 1250°C, are tested.
- the results are shown in the table 2.
- the thermal shrinkage is the average value of length, width and thickness. It is tested by placing the test specimens in an oven, heating to required temperature and maintaining for 3 hrs. The dimension change is measured after sample cooling down to ambient conditions.
- thermal shrinkage of test-1 is 1%, in contrast, that of FB 135 is 12.5%.
- the present invention (test 1) is shown superior to prior art, in terms of remarkably improved thermal shrinkage.
- the thermal shrinkage at high temperature is one of key parameters for the Fire test. If it is too high, the thin spray will crack and fire will go through via the crack openings, leading to material collapse and poor thermal insulation.
- test 3, test 4 Two further compositions (test 3, test 4) of the present invention (see table 3) and balanced water are mixed together by a planetary mixer to form a homogeneous cementitious mortar, then sprayed on a B35 concrete slab with 150mm thickness on ceiling by a spray machine, the spray is trowel finished to have a good surface aspect with an equal thickness of 27.5 mm. No metal meshes are used inside the spray.
- the B35 concrete has the minimum compressive strength of 35 MPa when cured at 28 days at 20°C.
- Full scale Rf RWS tests are made by placing the concrete slab on ceiling, side by side with the Promat PROMATECT ® -H board (PT-H board) at a thickness of 27.5mm.
- the PT-H board is known for tunnel fire protection, it usually passes the RWS test at 27.5mm thickness. It is used here as Benchmark.
- the Rf RWS test shows that the test-3 and test-4 compositions keep stable on ceiling during the whole period of fire test and even after cooling down.
- the maximum temperature (T max ) an average value of 5 thermal couples, is measured 356°C for PT-H board (reference), 348°C for the test-3, and 301°C for the test-4 of present invention. From statistic point of view, test-3 and the PT-H board have the same thermal insulation, the test-4 can pass the Rf RWS test at equal thickness of 27.5mm.
- the test-4 shows remarkably lower T max thanks to the effect of spherical Xonotlite, it is estimated to pass the Rf RWS test at 25mm thickness.
- XRD quantification program identifies crystalline phases Belite (C2S) 16.4%, Alite (C3S) 55.7%, Gehlenite (C2AS) 12.8%, others 15%. Mica, Calcite or CaO are not detected, as evidence that they have all reacted at the high temperatures. It is these refractory phases formed in situ that turn the cementitious mortar into a refractory mass with good thermal stability, that make it capable to pass the Rf RWS test with remarkably small thickness of ⁇ 27.5mm, compared to traditional sprays on the market.
- Freeze thaw test of the test-3 composition is made according to EN12467, by placing the water saturated sample into a refrigerator, exposing temperature change from 20°C to -20°C per cycle, 4 cycles per day, total for 100 cycles. During the test, no surface scalling or material delamination are observed.
- xonotlite When xonotlite is used, the mortar can be improved further in both thermal insulation (Max temperature in Tab. 4) and thermal stability (thermal shrinkage at 1250°C in Tab. 6).
- Xonotlite is a desirable component for the mortar of the invention.
- Example 3 analyzes the properties of the product described in CN101863640 A.
- Table 7 describes compositions prepared according to the disclosure of CN101863640 A . They are based on average formulations described in the document.
- MIX-1 uses a combination of expanded perlite, exfoliated vermiculite and Precipitated Calcium Carbonate (PCC).
- MIX-2 uses only expanded perlite and Precipitated Calcium Carbonate (PCC) without exfoliated vermiculite.
- Table 8 compares the density and the bending strength and the shrinkage of the materials with the material Test-3 of Example 2.
- Table 8: Results of comparison test density bending strength shrinkage at 1250°C g/cm 3 Mpa % MIX-1 0.774 1.2 28.8 MIX-2 0.665 1.0 melted Test-3 Invention 0.844 2.3 3.9
- Figure 3 shows a photo of the material after the fire test. According to the reference, the product must be able to withstand temperatures of a hydrocarbon fire. These test conditions require resistance at 1100°C, i.e. lower than the RWS fire curve (see figure 1 ). MIX-1 and MIX-2 do not withstand the RWS fire test.
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Claims (15)
- Composition pour la préparation d'un mortier de protection contre l'incendie comprenant- 45 à 70 % en poids de liant de ciment,- 8 à 20 % en poids de calcite,- 8 à 20 % en poids de mica,- 0 à 5 % en poids de xonotlite,- 0,1 à 20 % en poids de perlite expansée,- 0,1 à 10 % en poids de fibres,- 0,01 à 2 % en poids d'agent entraîneur d'air et moussant,- 0,01 à 4 % en poids d'adjuvants de fabrication.
- Composition selon la revendication 1, dans laquelle le liant de ciment est choisi dans le groupe constitué du ciment Portland (CEM I), du ciment composite Portland (CEM II), du ciment au laitier de haut fourneau (CEM III), du ciment pouzzolanique (CEM IV), d'un autre ciment composite (CEM V), et de leurs combinaisons.
- Composition selon la revendication 1 ou 2, dans laquelle le liant de ciment comprend du ciment d'aluminate de calcium, du ciment d'aluminate de soufre et leurs combinaisons.
- Composition selon les revendications 1 à 3, dans laquelle les fibres sont sélectionnées dans le groupe constitué d'une fibre de PP, d'une fibre de PVA, d'une fibre de cellulose, d'une fibre de verre dont une fibre de verre alcalinorésistante, d'une laine de roche, d'une laine minérale, d'une fibre d'acier et de leurs combinaisons.
- Composition selon les revendications 1 à 4, dan laquelle la perlite expansée est en partie ou entièrement substituée par des charges sélectionnées dans le groupe constitué de la ponce, du verre moussé, de l'argile expansée, de sphères céramiques creuses de cendres volantes provenant d'une centrale électrique, de la vermiculite exfoliée et de leurs combinaisons.
- Composition selon l'une quelconque des revendications 1 à 5, dans laquelle les adjuvants de fabrication sont sélectionnés dans le groupe constitué d'un retardateur de prise, d'un accélérateur de prise, d'un super plastifiant, d'un adjuvant de pompage, d'un agent de rétention de l'eau, d'un agent thixotrope, d'un hydrofuge, de polymères redispersibles et diluables à l'eau et de leurs combinaisons.
- Composition selon l'une quelconque des revendications 1 à 6, dans laquelle les fibres ont une longueur moyenne de moins de 15 mm.
- Composition selon l'une quelconque des revendications 1 à 7, dans laquelle la calcite a une taille de particule (d90 en poids) de moins de 200 µm.
- Mortier de protection contre l'incendie pouvant être obtenu par mélange de la composition de l'une quelconque des revendications 1 à 8 avec de l'eau, de préférence- 30 à 70 % en poids de la composition des revendications 1 à 8 et- 70 à 30 % d'eau.
- Produit de protection contre l'incendie pouvant être obtenu par pulvérisation ou coulage du mortier de protection contre l'incendie de la revendication 9.
- Produit de protection contre l'incendie selon la revendication 10, dans lequel le coulage inclut les processus de façonnage sélectionnés parmi les processus de filtre-presse, Flow-on et Magnani.
- Produit de protection contre l'incendie selon la revendication 10 ou 11, ayant une masse volumique apparente en dessous de 1 200 kg/m3, de préférence entre 500 et 1 000 kg/m3.
- Procédé de fourniture d'un système de protection contre l'incendie comprenant- la pulvérisation d'un mortier de la revendication 9 et/ou- le scellement d'un produit de protection contre l'incendie coulé de la revendication 11 ou 12sur un substrat.
- Procédé selon la revendication 13, comprenant en outre l'enrobage d'une toile métallique ou plastique dans le mortier.
- Utilisation d'une composition selon l'une quelconque des revendications 1 à 8, pour la préparation d'un mortier de protection contre l'incendie.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP14703051.4A EP2807130B1 (fr) | 2013-02-05 | 2014-02-03 | Mortier de protection contre l'incendie |
SI201430092A SI2807130T1 (sl) | 2013-02-05 | 2014-02-03 | Protipožarno zaščitna malta |
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EP13153960 | 2013-02-05 | ||
EP14703051.4A EP2807130B1 (fr) | 2013-02-05 | 2014-02-03 | Mortier de protection contre l'incendie |
PCT/EP2014/052002 WO2014122085A1 (fr) | 2013-02-05 | 2014-02-03 | Mortier antifeu |
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EP2807130A1 EP2807130A1 (fr) | 2014-12-03 |
EP2807130B1 true EP2807130B1 (fr) | 2016-08-24 |
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US (1) | US9034097B2 (fr) |
EP (1) | EP2807130B1 (fr) |
JP (1) | JP6332988B2 (fr) |
KR (1) | KR102119216B1 (fr) |
CN (1) | CN103964776B (fr) |
AU (1) | AU2014200344B2 (fr) |
BR (1) | BR102014002644B1 (fr) |
CA (1) | CA2840343C (fr) |
DK (1) | DK2807130T3 (fr) |
EA (1) | EA026204B1 (fr) |
ES (1) | ES2604658T3 (fr) |
HU (1) | HUE030978T2 (fr) |
LT (1) | LT2807130T (fr) |
MX (1) | MX357372B (fr) |
MY (1) | MY175739A (fr) |
PL (1) | PL2807130T3 (fr) |
PT (1) | PT2807130T (fr) |
SG (1) | SG2014007660A (fr) |
SI (1) | SI2807130T1 (fr) |
WO (1) | WO2014122085A1 (fr) |
ZA (1) | ZA201400662B (fr) |
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CN103964776B (zh) | 2016-07-06 |
US9034097B2 (en) | 2015-05-19 |
BR102014002644A8 (pt) | 2020-11-17 |
LT2807130T (lt) | 2017-03-10 |
ES2604658T3 (es) | 2017-03-08 |
JP6332988B2 (ja) | 2018-05-30 |
CA2840343C (fr) | 2021-02-23 |
SI2807130T1 (sl) | 2017-02-28 |
US20140216653A1 (en) | 2014-08-07 |
MY175739A (en) | 2020-07-07 |
KR20140100446A (ko) | 2014-08-14 |
AU2014200344A1 (en) | 2014-08-21 |
CA2840343A1 (fr) | 2014-08-05 |
BR102014002644B1 (pt) | 2021-06-01 |
MX2014001274A (es) | 2014-11-04 |
PT2807130T (pt) | 2016-12-06 |
EP2807130A1 (fr) | 2014-12-03 |
JP2014152101A (ja) | 2014-08-25 |
CN103964776A (zh) | 2014-08-06 |
EA201400102A1 (ru) | 2014-08-29 |
WO2014122085A1 (fr) | 2014-08-14 |
AU2014200344B2 (en) | 2017-03-02 |
MX357372B (es) | 2018-07-06 |
DK2807130T3 (en) | 2016-12-12 |
SG2014007660A (en) | 2014-09-26 |
BR102014002644A2 (pt) | 2015-12-08 |
KR102119216B1 (ko) | 2020-06-05 |
HUE030978T2 (en) | 2017-06-28 |
PL2807130T3 (pl) | 2017-03-31 |
EA026204B1 (ru) | 2017-03-31 |
ZA201400662B (en) | 2015-04-29 |
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